Methacryloyl Chloride Research Articles

Synthesis and characterization of potential multifunctional methacrylate-based dental monomers

We describe synthesis and characterization of a series of novel multifunctional methacrylate-based dental monomers. Triethanolamine was reacted with glycidyl methacrylate and methacryloyl chloride to produce a series of multifunctional methacrylate-end-capped compounds for conversion to quaternary ammonium fluoride monomers with decyl-substituted side-chain to afford antibacterial dental monomers. The chemical structure of all samples was characterized by Fourier-transform infrared and proton nuclear magnetic resonance (1H NMR) spectroscopies. The obtained monomers have potential to replace 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]propane as base monomer of universal resin-based dental composites in presence of diluting monomer (e.g., triethylene glycol dimethacrylate) due to their multifunctionality as well as possible antibacterial activity.

Synthesis of amphiphilic fluorescent copolymers with smart pH sensitivity via RAFT polymerization and their application in cell imaging

In this paper, a fluorescein methacryloyl monomer (named Flu-MA) was firstly fabricated by the esterification reaction of fluorescein and methacryloyl chloride; subsequently, a novel amphiphilic fluorescent copolymer (Flu-PEG) with smart pH sensitivity was successfully prepared by RAFT copolymerizing of Flu-MA and poly(ethylene glycol) monomethacrylate (PEGMA). The result of 1H NMR and FTIR implied that both Flu-MA and PEGMA monomers were successfully incorporated into Flu-PEG copolymers, the molecular weight (M n) of which was about 39,800 with polydispersity index (PDI) as about 1.30. In aqueous solution, Flu-PEG copolymers could self-assemble into fluorescent organic nanoparticles (FONs) with about 200 nm diameters due to high water dispersibility and good fluorescence, respectively, endowed by PEGMA and Flu-MA, the fluorescence intensity of which was high sensitive to pH value of solution. More importantly, due to their high water dispersibility, excellent biocompatibility and good fluorescence, the as-prepared Flu-PEG FONs were high attractive for the application in cell imaging. A novel amphiphilic fluorescent copolymer (Flu-PEG) with smart pH-sensitivity was successfully fabricated by RAFT copolymerizing of Flu-MA and PEGMA, which showed high water dispersibility, uniform size and excellent biocompatibility, making them be highly potential for bioimaging application.

Antibacterial N‐halamine coating on cotton fabric fabricated using mist polymerization

ABSTRACT3‐Methylallyloxy‐5,5‐dimethylhydantoin (MH), an methacrylate monomer containing N‐halamine moiety, was synthesized by 5,5‐dimethylhydantoin (DMH) and methacryloyl chloride. Antimicrobial coating of poly[1‐methyl‐1‐(4,4‐dimethyl‐2,5‐dioxoimidazolidin‐carbonyl)ethylene] (PMH) was prepared on cotton fabrics via “mist polymerization” using MH as monomer. The coating gave the cotton fabric with efficient antibacterial function with remarkable durability. In the antibacterial tests, the bacteriostatic reduction rate is greater than 99.78%, and can be maintained over 99.00% even after 30 washing cycles. Compared with other antimicrobial technologies, mist polymerization offers advantages such as achieving antimicrobial function by small consumption of monomer, forming coatings on single‐side of the fabrics, and minimizing the damages on the original properties of cotton during the finishing process. It can be applied in a wide variety of textile products such as sportswear, underwear, socks, and medical textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44897.

Sulfonyl hydrazide-based polymeric foaming agent nanoparticles

Polymeric foaming agent (PFA), poly(methacryloyl toluenesulfonylhydrazide) (poly(MATSH)), was synthesized from p-toluenesulfonyl hydrazide (TSH) with methacryloyl chloride (MAC) and transformed into nanoscale material by using a method of emulsion-solvent evaporation with polyvinyl alcohol (PVA) as an emulsifier. Average particle size of poly(MATSH) nanoparticle was determined by dynamic light scattering (DLS) and transmission electron microscopy (TEM), in comparison with TSH and MATSH monomer nanoparticles. Thermal decomposition temperature of the prepared nanoparticles was measured by using thermogravimetric analysis (TGA). A fraction of PVA remained in poly(MATSH) nanoparticle in spite of repeated washing increased decomposition temperature of the nanoparticles. The exothermic temperature of poly(MATSH) nanoparticle was examined by using differential scanning calorimetry (DSC). Furthermore, the polymer incorporated with poly(MATSH) nanoparticle according to foaming formulation based on styrene butadiene rubber (SBR) by compression molding showed higher expansion ratio due to higher surface volume and also made finer and more uniform cell structure due to smaller particle size and better compatibility with polymer and other fillers than those of poly(MATSH) in the morphology study of scanning electron microscopy (SEM).

Engineering of new spiropyran photochromic fluorescent polymeric nanoparticles of narrow size distribution by emulsion polymerization process

Spiropyran derivatized vinylic monomer (MSP) was prepared by coupling a typical spiropyran dye, 1′-(2-hydroxyethyl)-3′,3′-dimethyl-6-nitrospiro(2H-1-benzo-pyran-2,2′-indoline), to methacryloyl chloride. Poly(styrene-butylmethacrylate-divinylbenzene-MSP), P(S-BMA-DVB-MSP), photochromic fluorescent nanoparticles (NPs) of narrow size distribution were prepared by emulsion polymerization of the vinylic monomers: S, BMA, DVB and MSP. The influence of various polymerization parameters (e.g., concentration of the monomers, initiator and surfactant and pH) on the diameter, diameter distribution and photochromic fluorescence properties of the particles was elucidated.Spiropyran type molecules as well as MSP are colorless and non-fluorescent at the Spiro conformation. These compounds at the Merocyanine conformation are non-fluorescent in water or in non-polar organic solvents. However, when the Merocyanine conformation is entrapped within hydrophobic polymer particles, the particles exhibit blue color and strong red fluorescence.Absorbance and fluorescence measurements reveal that increasing the MSP or BMA relative concentration leads to a higher absorbance and fluorescence intensity of the formed P(S-BMA-DVB-MSP) NPs.Photoisomerization switching of the P(S-BMA-DVB-MSP) NPs was studied by exposing the NPs aqueous dispersion to alternating UV and visible light cycles. This study indicates 100% reversibility after five cycles of photoswitching.

Conductive inks based on methacrylate end‐capped poly(3,4‐ethylenedioxythiophene) for printed and flexible electronics

A new synthesis of methacrylate end‐capped poly(3,4‐ethylenedioxythiophene) (PEDOT) was performed: the polymer is soluble in common organic solvents, thus overcoming the well‐known technical problems related to the use of commercial PEDOT in different printing technologies, such as screen printing, due to its poor processability and compatibility in formulations with other resins and polymers. The new synthetic method developed is based on the direct oxidative polycondensation of 3,4‐ethylenedioxythiophene (EDOT) in the presence of an oxidant species and a crosslinkable end‐capper, i.e., methacrylate end‐capped EDOT (mEDOT), prepared via Friedel Crafts acylation with methacryloyl chloride. The oxidative polycondensation between EDOT and mEDOT monomers in the presence of a new kind of doping agent, Sulfonated Polyarylethersulfone (SPES)—characterized by different degree of sulfonation (DS)—was conducted, leading to functional end‐capped conducting PEDOT (mPEDOT_SPES), with conductivity of 210 S/cm, 50 S/cm higher than the one of commercial PEDOT. Thanks to the enhancement of solubility, leading to better processability, end‐capped PEDOTs were formulated with a thermoplastic ink, Plastisol®, and electronic circuits were successfully screen printed on flexible cotton substrates, to obtain printed crosslinkable electronic circuits. The conductive features of mPEDOT_SPESs were successfully compared with the ones of PEDOT and of not‐doped end‐capped PEDOTs. POLYM. ENG. SCI., 57:491–501, 2017. © 2017 Society of Plastics Engineers

Dielectric and spectroscopic properties of copolymers based on methacrylate carrying coumarin side group

ABSTRACTA methacrylic monomer 7–methacryloyloxy–4–methylcoumarin (MAOMC) was synthesized by reacting 7–hydroxy–4–methyl coumarin with methacryloyl chloride. Copolymerization of MAOMC with styrene (St), ethyl methacrylate (EMA), methyl methacrylate (MMA), n–butyl methacrylate (nBMA) and isobutyl methacrylate (IBMA) were performed by the free radical polymerization method (FRP) at low conversions. The resulting polymers were characterized by 1H NMR, FTIR, fluorescence and UV–vis spectroscopy. Dielectric properties of copolymers were measured by means of an impedance analyzer as a function of frequency and temperature. Dielectric measurements of copolymers prepared in a plate form were performed at room temperature over the frequency range 0.1 kHz–2 MHz and given as compared with each other. It was found that the dielectric constant of copolymers diminished in the applied frequency range. The optimized structural geometry and HOMO and LUMO energies of copolymers were carried out by density functional theory (DFT/B3LYP) method with 3−21G* as a basis set.

New approach in the application of lignin for the synthesis of hybrid materials

Abstract In this study, a novel method for the synthesis of hybrid, porous microspheres, including divinylbenzene (DVB), triethoxyvinylsilane (TEVS) and methacrylated lignin (L-Met), is presented. The methacrylic derivatives of kraft lignin were obtained by reaction with methacryloyl chloride according to a new experimental protocol. The course of the modification of lignin was confirmed by attenuated total reflectance (ATR-FTIR) and nuclear magnetic resonance (NMR) spectroscopy. The emulsion-suspension polymerization method was employed to obtain copolymers of DVD, TEVS and L-Met in spherical forms. The porous structures and morphologies of the obtained lignin-containing functionalized microspheres were investigated by low-temperature nitrogen adsorption data and scanning electron microscopy (SEM). The microspheres are demonstrated to be mesoporous materials with specific surface areas in the range of 430–520 m2/g. The effects of the lignin component on the porous structure, shape, swelling and thermal properties of the microspheres were evaluated.

UV-grafting coloration of cotton and wool fabrics using bismethacrylated quinizarin dye

A novel bifunctional quinizarin dye possessing two photoactive methacrylate groups was synthesized by the reaction of quinizarin with methacryloyl chloride. The synthesized dye, a low substantive dye under the conventional dyeing process, can be photografted onto cotton and wool fabrics at room temperature without neutral salts, which makes it a novel coloration process of excellent environmental friendliness. The concurrent polymerization and grafting of the synthesized dye onto cotton or wool can be assisted by a photoinitiator and acrylic acid in the case of cotton grafting. Moreover, color yields of the grafted fabrics improved significantly with the photografting of the bifunctional dye. The bifunctional dye can be photopolymerized with the increase in UV energy to 25 J/cm2 and the oligomeric dye has a degree of polymerization of 5 or more. Furthermore, the color fastness properties of the grafted fabrics were superior to those of the dyed fabrics via exhaustion.

Preparation of thermoresponsive fluorescent carbon dots for cellular imaging

Nowadays, carbon dots (CDs) have aroused widespread interest due to their chemical stability, biocompatibility as well as low toxicity. Herein, polymerizable CD monomers were synthesized through amidation between hydrophobic CDs and methacryloyl chloride, which has emerged as a facile method for preparing various fluorescent CD monomers. The fluorescent polymerizable CDs were copolymerized with N-isopropylacrylamide (NIPAM) to form thermoresponsive fluorescent nanoparticles. The poly(NIPAM) (PNIPAM) grafted hydrophobic CDs (CDs-g-PNIPAM) have excellent dispersivity in water, rendering hydrophobic CDs with fluorescence properties in aqueous media. Moreover, CDs-g-PNIPAM nanocomposites show a remarkable thermoresponsive behavior, and the fluorescence intensity decreases progressively with increase in temperature. Cytotoxicity tests show that CDs-g-PNIPAM nanocomposites have great biocompatibility. When the CDs-g-PNIPAM nanocomposites were cultured with HaCaT cells at a concentration of 2000 µg mL−1, cell viability was maintained over 85%. Benefiting from the copolymerization of NIPAM, the excitation-independent fluorescence of CDs-g-PNIPAM nanocomposites can be used for cellular labeling and show long-term biostability in a cellular environment. © 2016 Society of Chemical Industry

A study of experimental and theoretical analysis of N-cyclohexylmethacrylamide monomer based on DFT and HF computations

Purpose This paper aims to synthesise and characterise N-cyclohexylmethacrylamide (NCMA) monomer which contains thermosensitive group. The characterisation of monomer was performed both theoretically and experimentally. Design/methodology/approach The monomer was prepared by reacting cyclohexylamine with methacryloyl chloride in the presence of triethylamine at room temperature. The synthesised monomer was characterised by using not only Density Functional Theory (DFT) and Hartree–Fock (HF) with the Gaussian 09 software but also fourier transform infrared (FT–IR), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. Findings Both the experimental and the theoretical methods demonstrated that the monomer was successfully synthesised. The vibrational frequencies, the molecular structural geometry, such as optimised geometric bond angles, bond lengths and the Mulliken atomic charges of NCMA were investigated by using DFT/B3LYP and HF methods with the 3-21G* basis set. The experimental results were compared with theoretical values. The results revealed that the calculated frequencies were in good accord with the experimental values. Besides, frontier molecular orbitals (FMOs) and molecular electrostatic potential of NCMA were investigated by theoretical calculations at the B3LYP/3–21G* basis set. Research limitations/implications Monomer and polymer containing a thermosensitive functional group have attracted great interest from both industrial and academic fields. Their characterisation can provide great opportunities for polymer science by using DFT and HF methods. Originality/value The monomer containing a thermosensitive functional group and a various polymer may be prepared by using DFT and HF methods described in this paper. The calculated data are greatly important to provide insight into molecular analysis and then used in technological applications.

Surface modification of microcrystalline cellulose (MCC) and its application in LDPE‐based composites

ABSTRACTMicrocrystalline cellulose (MCC) was modified by grafting onto its surface ferulic acid, methacryloyl chloride and oleoyl chloride. The efficacy of the chemical modification was confirmed by X‐ray photoelectron spectroscopy. In addition, the size distribution of the cellulosic particles was investigated by optical microscopy and laser granulometry and its hydrophobicity was evaluated using a contact angle method. Finally, to investigate the affinity of modified MCC with a nonpolar polymer and to assess its potential as a biobased reinforcing filler, the modified MCC was compounded into low‐density polyethylene. An organic peroxide, dicumyl peroxide, was added at selected formulations to see if it could further enhance mechanical bonding between the polymer and the particulates. The dispersion was assessed by scanning electron microscopy. Mechanical properties were investigated through tensile testing while the melt rheology of the composites was monitored by small angle oscillatory shear rheology. The acylation modification of the MCC improved the dispersion within LDPE and enhanced the mechanical properties of the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44348.

Copolymerization and thermal study of the new methacrylate derivative of 2,4,6-trichlorophenol

In this study, 2,4,6-trichlorophenyl methacrylate (TClPhMA) was synthesized by the reaction of methacryloyl chloride with 2,4,6-trichlorophenol in the ice bath condition. The obtained monomer was extracted by chloroform and purified on a chromatography column. In order to confirm the chemical structure of the new compound, spectroscopic studies (ATR-FTIR, 1H NMR, 13C NMR and GC–MS) were undertaken. The obtained TClPhMA was copolymerized with commercially available monomers such as methyl methacrylate, styrene, 1,4-divinylbenzene and 2-hydroxymethyl methacrylate. The copolymers were obtained by bulk polymerization in which benzoyl peroxide was used as a free radical initiator. The thermal properties of the copolymers were investigated by differential scanning calorimetry and thermogravimetry.

PolyAdenine cryogels for fast and effective RNA purification

Cryogels are used effectively for many diverse applications in a variety of fields. The isolation or purification of RNA, one of the potential utilizations for cryogels, is crucial due to their vital roles such as encoding, decoding, transcription and translation, and gene expression. RNA principally exists within every living thing, but their tendency to denaturation easily is still the most challenging issue. Herein, we aimed to develop adenine incorporated polymeric cryogels as an alternative sorbent for cost-friendly and fast RNA purification with high capacity. For this goal, we synthesized the polymerizable derivative of adenine called as adenine methacrylate (AdeM) through the substitution reaction between adenine and methacryloyl chloride. Then, 2-hydroxyethyl methacrylate (HEMA)-based cryogels were prepared in a partially frozen aqueous medium by copolymerization of monomers, AdeM, and HEMA. The cryogels were characterized by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), surface area measurements, thermogravimetric analysis (TGA), and swelling tests. RNA adsorption experiments were performed via batch system while varying different conditions including pH, initial RNA concentration, temperature, and interaction time. We achieved high RNA adsorption capacity of cryogels, with the swelling ratio around 510%, as 11.86mg/g. The cryogels might be reused at least five times without significant decrease in adsorption capacity.

Kalkon İçerikli Metakrilat Polimerlerinin Sentezi, Karakterizasyonu, Termal, Dielektrik ve Floresans Özelliklerinin İncelenmesi

In this study, the (1‐benzofurane‐2‐yl)‐3‐oxo‐prop‐1‐en‐1‐yl]‐2‐methoxyphenyl 2‐methyl acrylate monomer were synthesized from the acylation reaction of this compound with methacryloyl chloride that commercially purchased. Free radicalic or atom transfer radical polymerization methods were used for preparation of copolymers. FT‐IR, 1H and 13C‐NMR techniques were used for structure characterization of polymers. The thermal behaviors of polymers were relatively investigated by DSC and TGA, and the results were compared with each other. The dielectric behaviors of polymers were investigated as a function of temperature and frequency. The results obtained were associated with their the structures. The spectroscopic properties of the polymers were investigated by UV‐Vis and fluorescence spectroscopies. Effects of the solvent polarity on emission measurement were investigated with fluorescence spectroscopy. Under cover of dimerization property of chalcone, the chalcone ended polymer was photodimerizatied.

Grafting polyethylene glycol dicrylate (PEGDA) to cell walls of poplar wood in two steps for improving dimensional stability and durability of the wood polymer composite

Abstract Polyethylene glycol (PEG) treatment is an effective approach to endow wood with higher dimensional stability (DS), which is still a concern under humid conditions. In this study, poplar wood was first treated with methacryloyl chloride to introduce methacryl groups in the cell wall. Then functional PEG served as modifier, and copolymerization was conducted in the second step to prepare PEG-diacrylate (PEGDA) modified samples. The resultant wood polymer composites (WPCs) were characterized by solid state NMR, field emission scanning electron microscopy (FE-SEM), and X-ray diffraction (XRD). The physical and mechanical properties of the WPCs were also evaluated, such as anti-swelling efficiency (ASE), water uptake, dynamic hydrophilicity (contact angles), and thermal stability. The results show that the copolymerized WPC achieved 51.4% ASE with leaching <3.0%. Moreover, the surface hardness and water resistance of the wood are also greatly improved.

Biomass Vanillin-Derived Polymeric Microspheres Containing Functional Aldehyde Groups: Preparation, Characterization, and Application as Adsorbent.

The contribution reports the first polymeric microspheres derived from a biomass, vanillin. It reacted with methacryloyl chloride, providing monomer vanillin methacrylate (VMA), which underwent suspension polymerization in aqueous media and yielded microspheres in high yield (>90 wt %). By controlling the N2 bubbling mode and by optimizing the cosolvent for dissolving the solid monomer, the microspheres were endowed with surface pores, demonstrated by SEM images and mercury intrusion porosimetry measurement. Taking advantage of the reactive aldehyde groups, the microspheres further reacted with glycine, thereby leading to a novel type of Schiff-base chelating material. The functionalized microspheres demonstrated remarkable adsorption toward Cu(2+) (maximum, 135 mg/g) which was taken as representative for metal ions. The present study provides an unprecedented class of biobased polymeric microspheres showing large potentials as adsorbents in wastewater treatment. Also importantly, the reactive aldehyde groups may enable the microspheres to be used as novel materials for immobilizing biomacromolecules, e.g. enzymes.

Determination of ractopamine in pork using a magnetic molecularly imprinted polymer as adsorbent followed by HPLC

A new magnetic molecularly imprinted polymers (MMIPs) for separation and concentration of ractopamine (RAC) were prepared using surface molecular imprinting technique with methacryloyl chloride as functional monomer and RAC as template. The MMIPs were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and vibrating sample magnetometer. The results of re-binding experiments indicated that the MMIPs had fast adsorption kinetics and could reach binding equilibrium within 20min, and the adsorption capacity of the MMIPs was 2.87-fold higher than that of the corresponding non-imprinted polymer. The selectivity of the MMIPs was evaluated according to its recognition to RAC and its analogues. The synthesized MMIPs were successfully applied to extraction, followed by high performance liquid chromatography to determine RAC in real food samples. Spiked recoveries ranged from 73.60% to 94.5%, with relative standard deviations of <11.17%.

Improving dimensional stability and durability of wood polymer composites by grafting polystyrene onto wood cell walls

Wood polymer composites (WPCs) were prepared in this study by grafting polystyrene onto poplar wood cell walls through free‐radical copolymerization methods. Methacryloyl chloride was first employed to cause swelling and react with the hydroxyl groups on the wood cell walls. Styrene monomers were then copolymerized with the methacryl groups in situ. The resultant WPCs were observed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The physical and mechanical properties of the composites, including dimensional stability, water uptake, dynamic hydrophilicity, surface hardness, and thermal stability, were also evaluated. Results suggest that methacryl groups and styrene were successfully copolymerized, and that the resultant copolymer was grafted onto the wood matrix through the reaction of methacryl groups and hydroxyl groups on wood components. Graft copolymerization not only significantly improved the interfacial compatibility between the polymer and wood substance, but also provided the wood with higher dimensional stability, better hydrophobic properties, and enhanced surface hardness. POLYM. COMPOS., 39:119–125, 2018. © 2016 Society of Plastics Engineers

Assesment of technical lignins for uses in biofuels and biomaterials: Structure-related properties, proximate analysis and chemical modification

The potential of organosolv and kraft eucalyptus and spruce lignin as feedstock for polymeric materials and biofuel applications was assessed. Proximate analysis was used to predict the heating values and char formation. Chemical modification, based on the esterification reaction with methacryloyl chloride, was applied to introduce vinyl groups into the lignin macromolecules for enhanced reactivity. Kraft eucalyptus and spruce lignins had a more condensed structure than organosolv lignins, which resulted in greater thermal stability for these lignins. For different species within the same process, the thermal parameters showed a correlation with certain structural and compositional parameters (ash and sugars content, molecular weight and degree of condensation). Organosolv spruce lignin produced the highest heating value of 24MJ/Kg, which is suitable for biofuel applications. The content of phenolic OH groups was higher for kraft lignins and especially higher for softwood lignins, both organosolv and kraft. The degree of methacrylation, estimated from the content of vinyl groups per C9 lignin unit, was significantly greater for organosolv lignins than for kraft lignins despite the higher OH-groups content in the latter.